FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2290873524> ?p ?o ?g. }

• W2290873524 abstract "This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M2M’(CO)4]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation. Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd0-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd0-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex. Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold. Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe4(μ4-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mossbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group. Appendix A discusses attempts to access [Fe3Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ3-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe3Ni(μ4-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe4S4] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster." @default.
• W2290873524 created "2016-06-24" @default.
• W2290873524 creator A5074859695 @default.
• W2290873524 date "2016-01-01" @default.
• W2290873524 modified "2023-09-26" @default.
• W2290873524 title "The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation" @default.
• W2290873524 doi "https://doi.org/10.7907/z9tb14vb." @default.
• W2290873524 hasPublicationYear "2016" @default.
• W2290873524 type Work @default.
• W2290873524 sameAs 2290873524 @default.
• W2290873524 citedByCount "0" @default.
• W2290873524 crossrefType "dissertation" @default.
• W2290873524 hasAuthorship W2290873524A5074859695 @default.
• W2290873524 hasConcept C106773901 @default.
• W2290873524 hasConcept C116569031 @default.
• W2290873524 hasConcept C161624437 @default.
• W2290873524 hasConcept C161790260 @default.
• W2290873524 hasConcept C170493617 @default.
• W2290873524 hasConcept C178790620 @default.
• W2290873524 hasConcept C185592680 @default.
• W2290873524 hasConcept C2776568683 @default.
• W2290873524 hasConcept C2777550763 @default.
• W2290873524 hasConcept C2778591166 @default.
• W2290873524 hasConcept C2778689049 @default.
• W2290873524 hasConcept C2779394022 @default.
• W2290873524 hasConcept C2780643102 @default.
• W2290873524 hasConcept C32909587 @default.
• W2290873524 hasConcept C544153396 @default.
• W2290873524 hasConcept C55493867 @default.
• W2290873524 hasConcept C71240020 @default.
• W2290873524 hasConceptScore W2290873524C106773901 @default.
• W2290873524 hasConceptScore W2290873524C116569031 @default.
• W2290873524 hasConceptScore W2290873524C161624437 @default.
• W2290873524 hasConceptScore W2290873524C161790260 @default.
• W2290873524 hasConceptScore W2290873524C170493617 @default.
• W2290873524 hasConceptScore W2290873524C178790620 @default.
• W2290873524 hasConceptScore W2290873524C185592680 @default.
• W2290873524 hasConceptScore W2290873524C2776568683 @default.
• W2290873524 hasConceptScore W2290873524C2777550763 @default.
• W2290873524 hasConceptScore W2290873524C2778591166 @default.
• W2290873524 hasConceptScore W2290873524C2778689049 @default.
• W2290873524 hasConceptScore W2290873524C2779394022 @default.
• W2290873524 hasConceptScore W2290873524C2780643102 @default.
• W2290873524 hasConceptScore W2290873524C32909587 @default.
• W2290873524 hasConceptScore W2290873524C544153396 @default.
• W2290873524 hasConceptScore W2290873524C55493867 @default.
• W2290873524 hasConceptScore W2290873524C71240020 @default.
• W2290873524 hasLocation W22908735241 @default.
• W2290873524 hasOpenAccess W2290873524 @default.
• W2290873524 hasPrimaryLocation W22908735241 @default.
• W2290873524 hasRelatedWork W1767606100 @default.
• W2290873524 hasRelatedWork W1776819642 @default.
• W2290873524 hasRelatedWork W1793341908 @default.
• W2290873524 hasRelatedWork W2339488583 @default.
• W2290873524 hasRelatedWork W2573121517 @default.
• W2290873524 hasRelatedWork W2587804083 @default.
• W2290873524 hasRelatedWork W2761840320 @default.
• W2290873524 hasRelatedWork W2766281980 @default.
• W2290873524 hasRelatedWork W2777171685 @default.
• W2290873524 hasRelatedWork W2807966540 @default.
• W2290873524 hasRelatedWork W2808971126 @default.
• W2290873524 hasRelatedWork W2948357821 @default.
• W2290873524 hasRelatedWork W2960603628 @default.
• W2290873524 hasRelatedWork W3011189555 @default.
• W2290873524 hasRelatedWork W3155878145 @default.
• W2290873524 hasRelatedWork W3201618463 @default.
• W2290873524 hasRelatedWork W3207784616 @default.
• W2290873524 hasRelatedWork W61971029 @default.
• W2290873524 hasRelatedWork W634739518 @default.
• W2290873524 hasRelatedWork W859373840 @default.
• W2290873524 isParatext "false" @default.
• W2290873524 isRetracted "false" @default.
• W2290873524 magId "2290873524" @default.
• W2290873524 workType "dissertation" @default.